Synthetic method for electrochemical oxidation of 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound

A carbonyl dithioketal and trifluoromethyl technology are applied in the synthesis field of electrochemical oxidation of 2-trifluoromethyl-α-carbonyl dithioketal compounds, and achieve the advantages of avoiding pollution, low cost and reaction conditions. mild effect

Pending Publication Date: 2022-03-22
NANTONG UNIVERSITY
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Problems solved by technology

However, the method of using electrochemical oxidation conditions to synthesize 2-trifluoromethyl-alpha-carbonyl dithioketene compounds has not been reported, and therefore, there is still a need to continue research and exploration.

Method used

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  • Synthetic method for electrochemical oxidation of 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound
  • Synthetic method for electrochemical oxidation of 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound
  • Synthetic method for electrochemical oxidation of 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound

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preparation example Construction

[0042] refer to Figure 1-Figure 16 , a kind of synthetic method of electrochemical oxidation 2-trifluoromethyl-alpha-carbonyl dithioketene compound, comprises the following steps:

[0043] A, sequentially add compound 1, compound 2, electrolyte and solvent in the reactor equipped with electrode sheet;

[0044] B, under open conditions, above-mentioned compound 1 and compound 2 are carried out stirring reaction under the condition of certain temperature and constant electric current;

[0045] After C, reaction finishes, decompression evaporates solvent and obtains crude product;

[0046] D. Purify by column chromatography to obtain 2-trifluoromethyl-α-carbonyl dithioketene compound 3.

Embodiment 1

[0048] 3,3-bis(methylthio)-1-(p-tolyl)-2-(trifluoromethyl)prop-2-en-1-one

[0049]

[0050] A carbon felt sheet (size: 10mm×10mm×0.3mm) was assembled as an anode and an iron sheet (size: 10mm×10mm×0.3mm) was used as a cathode in a 10mL electrolytic cell without a diaphragm, and compound 1 (α-carbonyl disulfide Ketal, 0.5mmol), compound 2 (sodium trifluoromethylsulfinate, 1.5mmol, 234mg), electrolyte tetra-n-butylammonium perchlorate (1.5mmol, 513mg), water 1mL, acetonitrile 6mL at constant current The reaction was stirred at room temperature under 10 mA for 4 hours. After the reaction, the resulting mixture was poured into 15 mL of water and extracted with dichloromethane (3×15 mL). The combined organic layers were washed with 15 mL of brine and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator, and the residue was purified by flash chromatography [silica gel, petroleum ether: ethyl acetate volume ratio (50-100): 1] to obtain 114.3 mg of the...

Embodiment 2

[0052] 1-(4-fluorophenyl)-3,3-bis(methylthio)-2-(trifluoromethyl)prop-2-en-1-one

[0053]

[0054] A carbon felt sheet (size: 10mm×10mm×0.3mm) was assembled as an anode and an iron sheet (size: 10mm×10mm×0.3mm) was used as a cathode in a 10mL electrolytic cell without a diaphragm, and compound 1 (α-carbonyl disulfide Ketal, 0.5mmol), compound 2 (sodium trifluoromethylsulfinate, 1.5mmol, 234mg), electrolyte tetra-n-butylammonium perchlorate (1.5mmol, 513mg), water 1mL, acetonitrile 6mL at constant current The reaction was stirred at room temperature under 10 mA for 4 hours. After the reaction, the resulting mixture was poured into 15 mL of water and extracted with dichloromethane (3×15 mL). The combined organic layers were washed with 15 mL of brine and dried over anhydrous sodium sulfate. The solvent was removed on a rotary evaporator, and the residue was purified by flash chromatography [silica gel, petroleum ether: ethyl acetate volume ratio (50-100): 1] to obtain 81.3 m...

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Abstract

The invention relates to the technical field of organic synthesis, in particular to a synthetic method for electrochemical oxidation of a 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound, which comprises the following steps: A, sequentially adding a compound 1, a compound 2, an electrolyte and a solvent into a reactor equipped with an electrode plate; b, carrying out stirring reaction on the compound 1 and the compound 2 under the conditions of certain temperature and constant current under an open condition; c, after the reaction is finished, decompressing and evaporating to remove the solvent to obtain a crude product; and D, carrying out column chromatography purification to obtain a 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound 3. According to the method, alpha-carbonyl ketene dithioacetal and sodium trifluoromethanesulfinate are used as raw materials, an anode electrode slice is a carbon felt electrode, a cathode electrode slice is an iron sheet electrode, the energizing current is 10 milliamperes, an electrolyte is a solvent formed by mixing tetra-n-butylammonium perchlorate and acetonitrile / water, and the reaction temperature is room temperature; the 2-trifluoromethyl-alpha-carbonyl ketene dithioacetal compound can be efficiently synthesized by the method; compared with a traditional synthesis method, the method has the advantages that the reaction condition is mild, and the method can be smoothly carried out at room temperature; the operation is simple, and all operations can be carried out in an open system; current is used as an oxidation method in the reaction, so that pollution of transition metal and a chemical oxidant is avoided; the raw materials are easy to obtain, the functional group compatibility is good, and the substrate application range is wide.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a synthesis method for electrochemically oxidizing 2-trifluoromethyl-α-carbonyl dithioketene compound. Background technique [0002] Fluorine-containing organic compounds are widely found in medicines, pesticides, dyes and functional materials. The introduction of fluorine atoms into drug active molecules can change drug metabolism pathways and metabolic rates, prolong the action time of drug active molecules in the body, and improve drug metabolism stability. At the same time, it can enhance the lipid solubility of active drug molecules and improve the bioavailability of drugs [(a) Muller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881; (b) Furuya, T.; Kamlet , A.S.; Ritter, T. Nature 2011, 473, 470]. On the other hand, the synthesis, structure modification and application of α-carbonyl dithioketene, which is also a valuable molecular building block in organic sy...

Claims

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Application Information

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IPC IPC(8): C25B3/07C25B3/23
CPCC25B3/07C25B3/23
Inventor 曾小宝顾清云程振凤
Owner NANTONG UNIVERSITY
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